Glyphosate

Acetonitrile (#271004,
99.8%, MW = 41.08 g/mol), acrylamide (#A9909, 99%, MW = 71.08 g/mol),
azobis(2-methylpropionitrile) (#441090, 98%, MW = 164.31 g/mol), glyphosate
(#45521, 98%, MW = 169.07 g/mol), N,N′-methylenebis(acrylamide) (#146072, 99%, MW = 154.17 g/mol),
toluene (#244511, 99.8%, MW = 92.14 g/mol), and trimethoxy(7-octen-1-yl)silane
(#452815, 80%, MW = 232.39 g/mol) were purchased from Merck (Poznan,
Poland). Ethanol (#BA6480111, 99.8%, MW = 46.08 g/mol) and isopropanol
(#BA1500111, 99.7%, MW = 60.11 g/mol) were from POCh (Warsaw, Poland).
Hydrogen peroxide (#118851934, analytical grade, MW = 34.01 g/mol)
and sulfuric acid (#115750013, 98%, MW = 98.08 g/mol) were procured
from Chempur (Piekary Slaskie, Poland). Acetone (#50-8123, 99.8%,
MW = 58.08 g/mol) was obtained from Linegal Chemicals (Warsaw, Poland).
Fused silica slides were provided by TedPella (GE124, #26009; Redding,
CA), while commercial fused silica microcapillaries were purchased
from Postnova (#FSS-Z-200280; Landsberg, Germany).

Four pesticides, viz. glyphosate, 2,4-D, chlorothalonil and dimethoate of ≥ 98% purity, were obtained from Merck. Acetonitrile and methanol (LC–MS grade), and certified standard chemicals (MS grade, ≥ 99.9% purity) like CaCl₂, KCl, formic acid, acetic acid, phosphoric acid, ammonium acetate and ammonium formate were also purchased from Merck. The commercial formulations of the selected pesticides, glyphosate (100 g L^‒1 isopropylamine salt) and 2,4-D amine 625 (625 g L^‒1 dimethylamine and diethanolamine salts), chlortan 720 (720 g L^‒1 chlorothalonil), dimethoate (400 g L^‒1 dimethoate), were obtained from CRT Raymond’s Warehouse (suppliers of pesticide products in Australia). Aliquots of 1000, 160, 133.33 and 250 μL of the commercial formulations were diluted to 1.0 L with Milli-Q water to obtain 100 mg L^‒1 stock solution of glyphosate and 2,4-D, chlorothalonil and dimethoate, respectively. Then, 1.0 mL of each pesticide solution (100 mg L^‒1) was applied to 20 g soil to provide a final concentration of 5 mg L^‒1.

Glyphosate (PESTANAL^®, analytical standard; CAS N. 1071-83-6; MW: 169.07), Imidacloprid (PESTANAL^®, analytical standard; CAS N. 138261-41-3; MW: 255.66), Imazalil (PESTANAL^®, analytical standard; CAS N. 35554-44-0; MW: 297.18), lamba-cyhalothrin (PESTANAL^®, analytical standard; CAS N. 91465-08-6: MW: 449.8), acetylcholinesterase from Electrophorus electricus (CAS N. 9000-81-1; E.C. 3.1.1.7), butyrylcholinesterase from equine serum (CAS N. 9001-08-5; E.C. 3.1.1.8), tyrosinase from mushroom (CAS N. 902-10-2; E.C. 1.14.18.1), acetylthiocholine iodide (CAS N. 1866-15-5; MW: 289.18), butyrylthiocholine iodide (CAS N. 1866-16-6; MW: 317.23), 5,5′-dithiobis(2-nitrobenzoic acid) (DTNB; CAS N. 69-78-3; MW: 396.35), 3,4-dihydroxy-L-phenylalanine (CAS N. 59-92-7; MW: 197.19) and kojic acid (CAS N. 501-30-4; MW: 142.11) were purchased from Merck (Darmstadt, Germany). All other reagents and salts were of analytical grade and were also obtained from Merck (Darmstadt, Germany).

Glyphosate, aminomethylphosphonic acid, and malonic acid were purchased from Merck (Darmstadt, Germany). Ammonia solution (30%) and methanol were purchased from Carlo Erba (Milan, Italy). Standard solutions of phosphorous (10,000 mg L⁻¹) were obtained from Inorganic Ventures (Lakewood, NJ, USA).
HPLC-grade water was obtained from an ultrapure water purification system (18.2 MΩ cm, ELGA PURELAB flex, Veolia Water Solutions and Technologies, Ontario, Canada).

Glyphosate (PESTANAL^®, analytical standard), Imidacloprid (PESTANAL^®, analytical standard) and Imazalil (PESTANAL^®, analytical standard) were purchased from Merck (Darmstadt, Germany). Versene, trypsin-EDTA, Dulbecco’s Modified Eagle Medium (DMEM), penicillin, streptomycin, sodium pyruvate, L-glutamine and foetal bovine serum (FBS) were obtained from Gibco (Alfagene, Invitrogen, Lisbon, Portugal). Alamar Blue^® was purchased from Invitrogen, Life-Technologies (Porto, Portugal).

Gold(III)chloride trihydrate, trisodium citrate dihydrate, hydroxylamine hydrochloride, glyphosate (N-(phosphonomethyl)glycine) powder, sodium nitrate, and cysteamine hydrochloride (≥98%) were provided by Merck. Silver nitrate was provided by Kemika (Zagreb, Croatia). All chemicals were of analytical grade and were used without further processing. High purity water with a resistivity of 18 MΩ cm⁻¹ was used for all experiments.

LC-MS grade methanol and water were obtained from VWR, Darmstadt, Germany. Quercetin dehydrate (≥95%, high performance liquid chromatography (HPLC)) was purchased from Enzo Life Sciences GmbH, Lörrach, Germany. Diclofenac (>99%) was obtained from Cayman Chemical Company, Ann Arbor, Michigan, MI, USA. Glyphosate (100 quality level, HPLC), gabapentin (200 quality level, HPLC), monuron (100 quality level, HPLC), chloridazon (100 quality level, HPLC), carbetamide (100 quality level, HPLC), metobromuron (100 quality level, HPLC), sotalol (≥98%), quinoxyfen (100 quality level, HPLC), metconazol (100 quality level, HPLC) and fenofibrate (≥99%) were obtained from Sigma, Darmstadt, Germany. Metformin (300 quality level, HPLC) was obtained from Fluka, Buchs, Switzerland. Furthermore, chlorbromuron (99.24%) and diazinon (99.53%) were obtained from Dr. Ehrenstorfer, Augsburg, Germany. Carbamazepine, 2,3-dihydro-2,3-dihydroxycarbamazepine, 10,11-dihydro-10,11-dihydroxy-carbamazepine, 10,11-dihydro-10-hydroxy-carbamazepine, 9-acridine carboxaldehyde and carbamazepine-10,11-epoxide were kindly provided by the German Research Center for Environmental Health, Comparative Microbiome Analysis (COMI), Helmholtz Centrum of Munich, Munich, Germany.